The invention relates to novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones, and to their preparation and use in functional perfumery and in fine perfumery.
Compounds with a musk odor are sought-after components in the fragrance industry. They are characterized both by their property of imparting radiance to perfume compositions and also by their ability to act as fixative. For this reason, musk fragrances are nowadays used in many perfume compositions.
Typical musk fragrances are characterized by a macrocyclic ring having 13 to 17 carbon atoms which carries a ketone or an ester as functional group. Moreover, macrocyclic musk fragrances which carry two functional group are also known, e.g. 1,7-dioxacycloalkan-8-ones (EP A 884,315). However, the functional groups of these molecules are distributed over both hemispheres of macrocycles. Preference is, however, given to macrocyclic compounds in which the functional groups are concentrated in one part of the molecule since, in so doing, a stronger bond to the active center of the receptor and, consequently, a lower threshold value can be expected.
Because the costs of starting materials for the preparation are sometimes high and because of the extremely high synthesis complexity, the number of macrocyclic compounds available to the perfumer for the composition of perfumes is relatively limited (K. Bauer, D. Garbe, H. Surburg, Common Fragrance and Flavor Materials, Wiley-VCH, 3rd Edition, 1997, 67 to 68 and 117 to 122). There is an urgent need for further macrocyclic compounds which can be prepared in an efficient synthesis from favorable starting materials and, moreover, extend the perfumer""s options with their original scent properties.
The class of nature-similar macrocyclic musk fragrances will become more and more important in the future since the synthetic musk compounds of the nitroaromatic and polycyclic series are persistent and lipophilic, meaning that these compounds accumulate in aquatic food chains and fatty tissue (H. Brunn, G. Rimkus, Ernxc3xa4hrungs-Umschau 1996, 43, 442 to 449; H. Brunn, G. Rimkus, Ernxc3xa4hrungs-Umschau 1997, 44, 4 to 9).
It was therefore the object to extend the raw material palette available for composing perfume through novel macrocyclic musk compounds with original odiferous properties.
Furthermore, it should be possible to prepare the novel musk fragrances in a cost-effective manner.
We have now found novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones of the formula 
in which
the dashed bond is a single or E/Z double bond,
where in the case of a double bond being present in the ring, the compounds can be in the E and Z form, and
compounds with a chiral center can be either in the (R) or (S) form, or else can be present as an enantiomer mixture,
R1 and R2 are identical or different and are hydrogen or lower alkyl,
x is a saturated alkylene chain having 1 to 4 carbon atoms and
y is a saturated alkylene chain having 4 to 10 carbon atoms,
where saturated compounds
in which R1 and R2 are hydrogen and x+y=11 carbon atoms and
in which R1 is methyl and R2 is hydrogen and x+y=8 carbon atoms, are excluded.
Lower alkyl generally means a saturated hydrocarbon radical having 1 to 6 carbon atoms. Examples which may be mentioned are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, hexyl and isohexyl.
Preferred radicals are hydrogen, methyl and ethyl.
An alkylene chain having 1 to 4 carbon atoms generally means methylene, ethylene, propylene and butylene.
Preference is given here to: methylene, ethylene and butylene.
An alkylene chain having 4 to 10 carbon atoms generally means butylene, pentylene, hexylene, heptylene, octylene, nonylene and decylene.
Preference is given here to: butylene, octylene and nonylene.
The novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention accordingly include 14- to 18-membered saturated or unsaturated, unsubstituted or lower-alkyl-substituted 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones.
Specifically, mention may be made of the following 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones:
1,4-dioxa-(E/Z)-9-cyclotetradecen-2-one
1,4-dioxacyclotetradecan-2-one
3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one
3-methyl-1,4-dioxacyclopentadecan-2-one
1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one
1,4-dioxacyclopentadecan-2-one
3-methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one
3-methyl-1,4-dioxacyclohexadecan-2-one
1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one
1,4-dioxacyclohexadecan-2-one
1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one
1,4-dioxa (E/Z)-7-cycloheptadecen-2-one
3-methyl-1,4-dioxa-(E/Z)-7-cyclohexadecen-2-one
3-methyl-1,4-dioxa-(E/Z)-7-cycloheptadecen-2-one
3-methyl-1,4-dioxacycloheptadecan-2-one
The 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention in which the functional groups are in close proximity to one another achieve said object in an ideal manner. As well as perfumistically interesting musk-like odor notes, they are characterized by very good adhesion, coupled with a low threshold value.
The saturated 1,4-dioxacycloalkan-2-ones, methyl-substituted in the 3 position, in particular 3-methyl-1,4-dioxacyclopentadecan-2-one and 3-methyl-1,4-dioxacyclohexadecan-2-one, have particularly attractive olfactory odor properties. They are characterized by a sweet, woody-ambergris, animalic, erogenous and thus very natural musk note. The olfactory profile of the unsaturated 3-methyl-1,4-dioxacyloalken-2-ones is very similar to that of the saturated compounds, although the intensity is lower. For comparison, the analogous 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones without methyl substitution in the 3 position have been synthesized. Surprisingly, in the case of the unsaturated 1,4-dioxacycloalken-2-ones, the erogenous and animalic aspects are pushed into the background in favor of metallic, pressing iron-like odor descriptions. The saturated 1,4-dioxacycloalkan-2-ones, by contrast, and here in particular 1,4-dioxacyclohexadecan-2-one are characterized again by a very nice natural musk-like character.
In contrast to the known 1,4-dioxacycloheptadecan-2-one and 3-methyl-1,4-dioxacyclotetradecan-2-one, the 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention surprisingly have a very much more natural musk note, coupled with nitromusk and ambrette musk aspects.
We have found a process for the preparation of novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones of the formula 
in which
the dashed bond is a single or E/Z double bond,
where in the case of a double bond being present in the ring, the compounds can be in the E and Z form, and
compounds with a chiral center can be either in the (R) or (S) form, or else can be present as an enantiomer mixture,
R1 and R2 are identical or different and are hydrogen or lower alkyl,
x is a saturated alkylene chain having 1 to 4 carbon atoms and
y is a saturated alkylene chain having 4 to 10 carbon atoms,
where saturated compounds
in which R1 and R2 are hydrogen and x+y=11 carbon atoms and
in which R1 is methyl and R2 is hydrogen and x+y=8 carbon atoms, are excluded, found,
which is characterized in that alkylcarboxylic acids or esters thereof which can be derivatized in the 2 position and are of the formula 
in which
R1 has the meaning given above, and
R3 is OH, Cl, Br and
R4 is OH, OMe or OEt,
are used, which, in the 1st step, are etherified, in a 2nd step are esterified and in a 3rd step the ring is closed by olefine metathesis to give the unsaturated 1,4-dioxacycloalken-2-ones, which are then optionally hydrogenated in a 4th step to give the saturated 1,4-dioxacycloalkan-2-ones.
In the 1st step, where R3=OH and R4=OMe or OEt, deprotonation is carried out with one equivalent of sodium hydride as base in tetrahydrofuran as solvent. 1.5 equivalents of the [lacuna],xcfx89-alkene halide are then added, after which the reaction mixture is refluxed, giving the 2-alkenyloxycarboxylic esters (Tetrahedron Lett. 1976, 17, 3535).
In the case of the xcex1-halocarboxylic acids (R3=Cl, Br and R4=OH) as starting compounds, 2 to 3 equivalents of sodium hydride are required, the xcex1,xcfx89-alkenol firstly being deprotonated before the xcex1-halocarboxylic acid is added. This mixture too is refluxed in order to obtain the 2-alkenyloxycarboxylic acids (J. Org. Chem. 1998, 63, 3160).
The 2-alkenyloxycarboxylic acids (R4=OH) synthesized in the manner described above are esterified in the 2nd step with the addition of from 1 to 3 equivalents of the corresponding xcex1,xcfx89-alkenol and 0.1 to 5 mol % of p-toluenesulfonic acid with a water separator using toluene as entrainer to give the doubly terminally unsaturated 2-alkenyloxycarboxylic alkenyl esters.
If the 2-alkenyloxycarboxylic esters (R4=OMe, OEt) are present, these are firstly hydrolyzed with 1.5 to 2 equivalents of LiOH in methanol/water (ratio:3:1) in order then to be esterified with 1 to 3 equivalents of the corresponding xcex1,xcfx89-alkenol and 0.1 to 5 mol % of 0p-toluenesulfonic acid with a water separator to give the doubly terminally unsaturated 2-alkenyloxycarboxylic alkenyl esters.
The intermediates which form here are the novel doubly terminally unsaturated 2-alkenyloxycarboxylic alkenyl esters of the formula 
in which R1, R2, x and y have the meaning given above.
The 1,4-dioxacycloalken-2-ones according to the invention are prepared (3rd step) starting from the doubly terminally unsaturated 2-alkenyloxycarboxylic alkenyl esters in a ring closure olefin metathesis (U.S. Pat. No. 4,490,404; D. Tetrahedron lett., 1980, 21, 1715; JP 10 175,882). For this, the 2-alkenyloxycarboxylic alkenyl ester is refluxed for one hour in a 0.01 to 0.003 molar dichloromethane solution with 0.1 to 0.5 equivalents of titanium tetraisopropoxide. The subsequent addition of from 0.5 to 5 mol % of benzylidene-bis-tricyclohexylphosphine)-dichlororuthenium (Grubbs catalyst) and reheating at reflux temperature for 8 to 48 hours (Synthesis, 1997, 792; Synlett, 1997, 1010) produces the 1,4-dioxacycloalken-2-ones according to the invention.
The hydrogenation (4th step) at standard hydrogen pressure and room temperature with 1 to 5% by weight of Pd/C in isopropanol produces the 1,4-dioxacycloalkan-2-ones according to the invention starting from the 1,4-dioxacycloalken-2-ones according to the invention.
The process according to the invention can be illustrated using the example of 3-methyl-1,4-dioxacyclopentadecan-2-one by the following equation: 
We have found a further process for the preparation of the novel chiral 3-alkyl-1,4-dioxacycloalkan-2-ones and 3-alkyl-1,4-dioxacycloalken-2-ones of the formula 
in which the dashed bond is a single or E/Z double bond,
where in the case of a double bond being present in the ring, the compounds can be in the E and Z form,
and the compounds with a chiral center are present in the (R) or (S) form,
R1 is lower alkyl and
x is a saturated alkylene chain having 1 to 4 carbon atoms and
y is a saturated alkylene chain having 4 to 10 carbon atoms,
which is characterized in that the starting materials used are (S)-2- or (R)-2-hydroxycarboxylic alkyl esters of the formula 
in which
R1 has the meaning given above, and
R5 is a C1 to C8 alkyl radical,
which are etherified in a 1st step under acidic, nonracemizing conditions, are transesterified in a 2nd step under Lewis acid catalysis and in a 3rd step the ring is closed by olefin metathesis to give the unsaturated 3-alkyl-1,4-dioxacycloalken-2-ones, which are then optionally hydrogenated in a 4th step to give the saturated 3-alkyl1,4-dioxacycloalkan-2-ones.
In the 1st step, the O-alkylation of the (R)- or (S)-2-hydroxycarboxylic alkyl esters is carried out via the trichloroacetimidate methods (Tetrahedron Lett., 1988, 29, 4139-4142). For this, 2 to 3 equivalents of the alkenyl trichloroacetimidate and 5 to 15 mol % of trifluoromethanesulfonic acid are added to the chiral 2-hydroxycarboxylic alkyl esters in cyclohexane. After 16 to 24 hours at room temperature, the chiral (R)- or (S)-2-alkenyloxycarboxylic alkyl esters are obtained. The enantiomeric excesses of these compounds are xe2x89xa795%.
In the subsequent transesterification (2nd step), the chiral 2-alkenyloxycarboxylic ester is reacted with 1 to 3 equivalents of the corresponding [lacuna],xcfx89-alkenol, with the addition of from 1 to 10 mol % of titanium tetraisopropoxide (Tetrahedron Lett., 1998, 4223-4226). This gives the chiral, doubly terminally unsaturated 2-alkenyloxycarboxylic alkenyl esters.
The chiral doubly terminally unsaturated 2-alkenyloxycarboxylic alkenyl esters of the formula 
in which R1xe2x80x2, x and y have the meaning given above are novel.
The enantiomeric excesses of these compounds are xe2x89xa795%.
The preparation of the novel chiral 3-alkyl-1,4-dioxacycloalken-2-ones and 3-alkyl-1,4-dioxacycloalkan-2-ones is carried out in accordance with the methods described above, via ring closure olefin metathesis (3rd step) and subsequent hydrogenation (4th step).
The enantiomeric excesses of the saturated 3-alkyl-1,4-dioxacycloalkan-2-ones are xe2x89xa795%.
The process according to the invention can be illustrated using the example of (S)-(xe2x88x92)-3-methyl-1,4-dioxacyclopentadecan-2-one by the following equation: 
Specifically, the following chiral 3-alkyl-1,4-dioxacycloalkan-2-ones and 3-alkyl-1,4-dioxacycloalken-2-ones may be mentioned:
(S)-(xe2x88x92)-3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one
(S)-(xe2x88x92)-3-methyl-1,4-dioxacyclopentadecan-2-one
(S)-(xe2x88x92)-3-methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one
(S)-(xe2x88x92)-3-methyl-1,4-dioxacyclohexadecan- 2-one
(R)-(+)-3-methyl-1,4-dioxa-(E/Z)-6-cyclopentadecen-2-one
(R)-(+)-3-methyl-1,4-dioxacyclopentadecan-2-one
(R)-(+)-3-methyl-1,4-dioxa-(E/Z)-6-cyclohexadecen-2-one
(R)-(+)-3-methyl-1,4-dioxacyclohexadecan-2-one
The novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones can be used here as individual substances in a large number of products; they can be particularly advantageously combined with other fragrances to give new types of perfume compositions.
By using the novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones, it is generally possible, even in a low concentration, to achieve fine, erogenous musk notes in the resulting perfume compositions, the overall odor impression being remarkably harmonized, the radiance be detectably increased and the fixing, i.e. the adhesive power of the perfume oil, being considerably intensified.
Examples of fragrances with which the novel 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones can be advantageously combined are given, for example, in S. Arctander, Perfume and Flavor Materials, Vol. I and II, Montclair, N. J., 1969, Selbstverlag oder K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 3rd. Ed., Wiley-VCH, Weinheim 1997.
Specifically, mention may be made of:
extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures, such as, for example, ambergris tincture; amyris oil; angelica seed oil; angelica root oil; aniseed oil; valerian oil; basil oil; wood moss absolute; bay oil; mugwort oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savory oil; bucco leaf oil; cabreuva oil; cade oil; calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassia absolute; castoreum absolute; cedar leaf oil; cedarwood oil; cistus oil; citronella oil; lemon oil; copaiva balsam; copaiva balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; davana oil; dill herb oil; dill seed oil; eau de brouts absolute; oakmoss absolute; elemi oil; estragon oil; eucalyptus citriodora oil; eucalyptus oil; fennel oil; spruce needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiac wood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calamus oil; blue camomile oil; Roman camomile oil; carrot seed oil; cascarilla oil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; distilled lime oil; pressed lime oil; linaloe oil; litsea cubeba oil; bayleaf oil; mace oil; marjoram oil; mandarin oil; massoi bark oil; mimosa absolute; musk seed oil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove flower oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange-flower absolute; orange oil; origanum oil; palmarosa oil; patchouli oil; perilla oil; Peruvian balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; pimento oil; pine oil; pennyroyal oil; rose absolute; rosewood oil; rose oil; rosemary oil; Dalmation sage oil; Spanish sage oil; sandalwood oil; celery seed oil; spike lavender oil; Japanese anise oil; styrax oil; tagetes oil; fir needle oil; tea-tree oil; turpentine oil; thyme oil; Tolu balsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetiver oil; juniper oil; wine lees oil; absinthe oil; wintergreen oil; ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil; and fractions thereof, or ingredients isolated therefrom;
individual fragrances from the group of hydrocarbons, such as, for example, 3-carene; xcex1-pinene; xcex2-pinene; xcex1-terpinene; xcex3-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; farnesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene;
of aliphatic alcohols, such as, for example, hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methylheptanol, 2-methyloctanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; of aliphatic aldehydes and 1,4-dioxacycloalken-2-ones thereof, such as, for example, hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyl oxyacetaldehyde;
of aliphatic ketones and oximes thereof, such as, for example, 2-heptanone; 2-octanone; 3-octanone; 2-nonanone; 5-methyl-3-heptanone; 5-methyl-3-heptanone oxime; 2,4,4,7-tetramethyl-6-octen-3-one; of aliphatic sulfur-containing compounds, such as, for example, 3-methylthiohexanol; 3-methylthiohexyl acetate; 3-mercapto-hexanol; 3-mercaptohexyl acetate; 3-mercaptohexyl butyrate; 3-acetylthiohexyl acetate; 1-menthene-8-thiol; of aliphatic nitriles, such as, for example, 2-nonenenitrile; 2-tridecenenitrile; 2,12-tridecienenitrile; 3,7-dimethyl-2,6-octadienenittile; 3,7-dimethyl-6-octenenitrile;
of aliphatic carboxylic acids and esters thereof, such as, for example, (E)- and (Z)-3-hexenyl formate; ethyl acetoacetate; isoamyl acetate; hexyl acetate; 3,5,5-trimethylhexyl acetate; 3-methyl-2-butenyl acetate; (E)-2-hexenyl acetate; (E)- and (Z)-3-hexenyl acetate; octyl acetate; 3-octyl acetate; 1-octen-3-yl acetate; ethyl butyrate; butyl butyrate; isoamyl butyrate; hexyl butyrate; (E)- and (Z)-3-hexenyl isobutyrate; hexyl crotonate; ethyl isovalerate; ethyl 2-methylpentanoate; ethyl hexanoate; allyl hexanoate; ethyl heptanoate; allyl heptanoate; ethyl octanoate; ethyl (E,Z)-2,4-decadienoate; methyl 2-octynate; methyl 2-nonynate; allyl 2-isoamyloxy-acetate ; methyl 3,7-dimethyl-2,6-octadienoate;
of acyclic terpene alcohols, such as, for example, citronellol; geraniol; nerol; linalool; lavadulol; nerolidol; farnesol; tetrahydrolinalool; tetrahydrogeraniol; 2,6-dimethyl-7-octen-2-ol; 2,6-dimethyloctan-2-ol; 2-methyl-6-methylene-7-octen-2-ol; 2,6-dimethyl-5,7-octadien-2-ol; 2,6-dimethyl-3,5- octadien-2-ol; 3,7-dimethyl-4,6-octadien-3-ol; 3,7-dimethyl- 1,5,7-octatrien-3-ol 2,6-dimethyl-2,5,7-octatrien-1-ol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates thereof;
of acyclic terpene aldehydes and ketones, such as, for example, geranial; neral; citronellal; 7-hydroxy-3,7-dimethyloctanal; 7-methoxy-3,7-dimethyloctanal; 2,6,10-trimethyl-9-undecenal; geranyl acetone; and the dimethyl and diethyl acetals of geranial, neral, 7-hydroxy-3,7-dimethyloctanal;
of cyclic terpene alcohols, such as, for example, menthol; isopulegol; alpha-terpineol; terpineol-4; menthan-8-ol; menthan-1-ol; menthan-7-ol; borneol; isoborneol; linalool oxide; nopol; cedrol; ambrinol; vetiverol; guaiol; and formates, acetates, propionates, isobutyrates, butyrates, isovalerates, pentanoates, hexanoates, crotonates, tiglinates, 3-methyl-2-butenoates thereof;
of cyclic terpene aldehydes and ketones, such as, for example, menthone; isomenthone; 8-mercaptomenthan-3-one; carvone; camphor; fenchone; alpha-ionone; beta-ionone; alpha-n-methylionone; beta-n-methylionone; alpha-isomethylionone; beta-isomethylionone; alpha-irone; alpha-damascone; beta-damascone; beta-damascenone; delta-damascone; gamma-damascone; 1-(2,4,4-trimethyl-2-cyclohexen-1-yl)-2-buten-1-one; 1,3,4,6,7,8a-hexahydro-1,1,5,5-tetramethyl-2H -2,4a-methanonaphthalen-8(5H)-one; nootkatone; dihydronootkatone; alpha-sinensal; beta-sinensal; acetylated cedarwood oil (methyl cedryl ketone);
of cyclic alcohols, such as, for example, 4-tert-butylcyclohexanol; 3,3,5-trimethyl-cyclohexanol; 3-isocamphylcyclohexanol; 2,6,9-trimethyl-Z2,Z5,E9-cyclo dodecatrien-1-ol; 2-isobutyl-4-methyltetrahydro-2H-pyran-4-ol;
of cycloaliphatic alcohols, such as, for example, alpha,3,3-trimethylcyclohexyl -methanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent-1-yl)butanol; 2-methyl-4-(2,2,3-trimethyl-3-cyclopent- 1-yl)-2-buten-1-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopent- 1-yl)-2-buten-1-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-pentan-2-ol; 3-methyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopent-1-yl)-4-penten-2-ol; 1-(2,2,6-trimethylcyclohexyl)pentan-3-ol; 1-(2,2,6-trimethylcyclohexyl)hexan-3-ol;
of cyclic and cycloaliphatic ethers, such as, for example, cineol; cedryl methyl ether; cyclododecyl methyl ether; (ethoxymethoxy)cyclododecane; alpha-cedrene epoxide; 3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; 3a-ethyl-6,6,9a-trimethyl -dodecahydronaphtho[2,1-b]furan; 1,5,9-trimethyl-13-oxabicyclo[10.1.0]trideca-4,8-diene; rose oxide; 2-(2,4-dimethyl-3-cyclohexen-1-yl)-5-methyl-5-(1-methylpropyl)-1,3-dioxane;
of cyclic ketones, such as, for example, 4-tert-butylcyclohexanone; 2,2,5-trimethyl-5-pentylcyclopentanone; 2-heptylcyclopentanone; 2-pentylcyclopentanone; 2-hydroxy-3-methyl-2-cyclopenten-1-one; 3-methyl-cis-2-penten-1-yl-2-cyclopenten-1-one; 3-methyl-2-pentyl-2-cyclopenten-1-one; 3-methyl-4-cyclopentadecenone; 3-methyl-5-cyclopentadecenone; 3-methylcyclopentadecanone; 4-(1-ethoxyvinyl)-3,3,5,5-tetramethylcyclohexanone; 4-tert-pentylcyclohexanone; 5-cyclohexadecen-1-one; 6,7-dihydro-1,1,2,3,3-pentamethyl-4(5H)-indanone; 5-cyclohexadecen-1-one; 8-cyclohexadecen-1-one; 9-cycloheptadecen-1-one; cyclopentadecanone;
of cycloaliphatic aldehydes, such as, for example, 2,4-dimethyl-3-cyclohexene-carbaldehyde; 2-methyl-4-(2,2,6-trimethyl-cyclohexen-1-yl)-2-butenal; 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarbaldehyde; 4-(4-methyl-3-penten-1-yl)-3-cyclo-hexenecarbaldehyde;
of cycloaliphatic ketones, such as, for example, 1-(3,3-dimethylcyclohexyl)-4-penten-1-one; 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one; 2,3,8,8-tetramethyl-1,2,3,4,5,6,7,8-octahydro-2-naphthalenyl methyl ketone; methyl-2,6,10-trimethyl-2,5,9-cyclododecatrienyl ketone; tert-butyl 2,4-dimethyl-3-cyclohexen-1-yl ketone;
of esters of cyclic alcohols, such as, for example, 2-tert-butylcyclohexyl acetate; 4-tert-butylcyclohexyl acetate; 2-tert-pentylcyclohexyl acetate; 4-tert-pentylcyclohexyl acetate; decahydro-2-naphthyl acetate; 3-pentyltetrahydro-2H-pyran-4-yl acetate; decahydro-2,5,5,8a-tetramethyl-2-naphthyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexa-hydro-5 or 6-indenyl acetate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl propionate; 4,7-methano-3a,4,5,6,7,7a-hexahydro-5 or 6-indenyl isobutyrate; 4,7-methanooctahydro-5 or 6-indenyl acetate;
of esters of cycloaliphatic carboxylic acids, such as, for example, allyl 3-cyclohexyl-propionate; allyl cyclohexyloxyacetate; methyl dihydrojasmonate; methyl jasmonate; methyl 2-hexyl-3-oxocyclopentanecarboxylate; ethyl 2-ethyl-6,6-dimethyl-2-cyclo-hexenecarboxylate; ethyl 2,3,6,6-tetramethyl-2-cyclohexenecarboxylate; ethyl 2-methyl-1,3-dioxolan-2-acetate;
of aromatic hydrocarbons, such as, for example, styrene and diphenylmethane;
of araliphatic alcohols, such as, for example, benzyl alcohol; 1-phenylethyl alcohol; 2-phenylethyl alcohol; 3-phenylpropanol; 2-phenylpropanol; 2-phenoxyethanol; 2,2-dimethyl-3-phenylpropanol; 2,2-dimethyl-3-(3-methylphenyl)propanol; 1,1-dimethyl-2-phenylethyl alcohol; 1,1-dimethyl-3-phenylpropanol; 1-ethyl-1-methyl-3-phenylpropanol; 2-methyl-5-phenylpentanol; 3-methyl-5-phenylpentanol; 3-phenyl-2-propen-1-ol; 4-methoxybenzyl alcohol; 1-(4-isopropylphenyl)ethanol;
of esters of araliphatic alcohols and aliphatic carboxylic acids, such as, for example, benzyl acetate; benzyl propionate; benzyl isobutyrate; benzyl isovalerate; 2-phenylethyl acetate; 2-phenylethyl propionate; 2-phenylethyl isobutyrate; 2-phenylethyl isovalerate; 1-phenylethyl acetate; alpha-trichloromethylbenzyl acetate; alpha,alpha-dimethylphenylethyl acetate; alpha,alpha-dimethylphenylethyl butyrate; cinnamyl acetate; 2-phenoxyethyl isobutyrate; 4-methoxybenzyl acetate; of araliphatic ethers, such as, for example, 2-phenylethyl methyl ether; 2-phenylethyl isoamyl ether; 2-phenylethyl 1-ethoxyethyl ether; phenylacetaldehyde dimethyl acetal; phenylacetaldehyde diethyl acetal; hydratropaaldehyde dimethyl acetal; phenylacetaldehyde glycerol acetal; 2,4,6-trimethyl-4-phenyl-1,3-dioxanes; 4,4a,5,9b-tetrahydroindeno[1,2-d]-m-dioxin; 4,4a,5,9b-tetrahydro-2,4-dimethylindeno[1,2-d]-m-dioxin;
of aromatic and araliphatic aldehydes, such as, for example, benzaldehyde; phenyl-acetaldehyde; 3-phenylpropanal; hydratropaaldehyde; 4-methylbenzaldehyde; 4-methylphenylacetaldehyde; 3-(4-ethylphenyl)-2,2-dimethylpropanal; 2-methyl-3-(4-isopropylphenyl)propanal; 2-methyl-3-(4-tert-butylphenyl)propanal; 3-(4-tert-butylphenyl)propanal; cinnamaldehyde; alpha-butylcinnamaldehyde; alpha-amyl-cinnamaldehyde; alpha-hexylcinnamaldehyde; 3-methyl-5-phenylpentanal; 4-methoxybenzaldehyde; 4-hydroxy-3-methoxybenzaldehyde; 4-hydroxy-3-ethoxybenzaldehyde; 3,4-methylenedioxybenzaldehyde; 3,4-dimethoxybenzaldehyde; 2-methyl-3-(4-methoxyphenyl)propanal; 2-methyl-3-(4-methylenedioxyphenyl) -propanal;
of aromatic and araliphatic ketones, such as, for example, acetophenone; 4-methylacetophenone; 4-methoxyacetophenone; 4-tert-butyl-2,6-dimethylacetophenone; 4-phenyl-2-butanone; 4-(4-hydroxyphenyl)-2-butanone; 1-(2-naphthalenyl) -ethanone; benzophenone; 1,1,2,3,3,6-hexamethyl-5-indanyl methyl ketone; 6-tert-butyl-1,1-dimethyl-4-indanyl methyl ketone; 1-[2,3-dihydro-1,1,2,6-tetramethyl-3-(1-methylethyl)-1H-5-indenyl]ethanone; 5xe2x80x2,6xe2x80x2,7xe2x80x2,8xe2x80x2-tetrahydro-3xe2x80x2,5xe2x80x2,5xe2x80x2,6xe2x80x2,8xe2x80x2,8xe2x80x2-hexamethyl-2-acetonaphthone;
of aromatic and araliphatic carboxylic acids and esters thereof, such as, for example, benzoic acid; phenylacetic acid; methyl benzoate; ethyl benzoate; hexyl benzoate; benzyl benzoate; methyl phenylacetate; ethyl phenylacetate; geranyl phenylacetate; phenylethyl phenylacetate; methyl cinnmate; ethyl cinnamate; benzyl cinnamate; phenylethyl cinnamate; cinnamyl cinnamate; allyl phenoxyacetate; methyl salicylate; isoamyl salicylate; hexyl salicylate; cyclohexyl salicylate; cis-3-hexenyl salicylate; benzyl salicylate; phenylethyl salicylate; methyl 2,4-dihydroxy-3,6-dimethylbenzoate; ethyl 3-phenylglycidate; ethyl 3-methyl-3-phenylglycidate;
of nitrogen-containing aromatic compounds, such as, for example, 2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene; 3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone; cinnamonitrile; 5-phenyl-3-methyl-2-pentenenitrile; 5-phenyl-3-methylpentanenitrile; methyl anthranilate; methy N-methylanthranilate; Schiff bases of methyl anthranilate with 7-hydroxy-3,7-dimethyloctanal, 2-methyl-3-(4-tert-butylphenyl)propanal or 2,4-dimethyl-3-cyclohexenecarbaldehyde; 6-isopropylquinoline; 6-isobutylquinoline; 6-sec-butylquinoline; indole; skatole; 2-methoxy-3-isopropylpyrazine; 2-isobutyl-3-methoxypyrazine;
of phenols, phenyl ethers and phenyl esters, such as, for example, estragole; anethole; eugenole; eugenyl methyl ether; isoeugenole; isoeugenyl methyl ether; thymol; carvacrol; diphenyl ether; beta-naphthyl methyl ether; beta-naphthyl ethyl ether; beta-naphthyl isobutyl ether; 1,4-dimethoxybenzene; eugenyl acetate; 2-methoxy-4-methylphenol; 2-ethoxy-5-(1-propenyl)phenol; p-cresyl phenylacetate;
of heterocyclic compounds, such as, for example, 2,5-dimethyl-4-hydroxy-2H-furan-3-one; 2-ethyl-4-hydroxy-5-methyl-2H-furan-3-one; 3-hydroxy-2-methyl-4H-pyran-4-one; 2-ethyl-3-hydroxy-4H-pyran-4-one;
of lactones, such as, for example, 1,4-octanolide; 3-methyl-1,4-octanolide; 1,4-nonanolide; 1,4-decanolide; 8-decen-1,4-olide; 1,4-undecanolide; 1,4-dodecanolide; 1,5-decanolide; 1,5-dodecanolide; 1,15-pentadecanolide; cis- and trans-11-pentadecen-1,15-olide; cis- and trans-12-pentadecen-1,15-olide; 1,16-hexadecanolide; 9-hexadecen-1,16-oide; 10-oxa-1,16-hexadecanolide; 11-oxa-1,16-hexadecanolide; 12-oxa-1,16-hexadecanolide; ethylene 1,12-dodecanedioate; ethylene 1,13-tridecanedioate; coumarin; 2,3-dihydrocoumarin; octahydrocoumarin.
The perfume oils comprising the 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention can be used in liquid form, neat or diluted with a solvent for perfumings. Suitable solvents for this purpose are, for example, ethanol, isopropanol, diethylene glycol monoethyl ether, glycerol, propylene glycol, 1,2-butylene glycol, dipropylene glycol, diethyl phthalate, triethyl citrate, isopropyl myristate etc.
In addition, the perfume oils comprising the 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention can be adsorbed on a carrier which serves both to distribute the fragrances finely within the product and to release them in a controlled manner during use. Such carriers can be porous inorganic materials such as light sulfate, silica gels, zeolites, gypsums, clays, clay granules, gas concrete etc. or organic materials such as woods and cellulose-based substances.
The perfume oils comprising the 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention can also be microencapsulated, spray dried, in the form of inclusion complexes or in the form of extrusion products and be added in this form to the product to be perfumed.
The properties of the perfume oils modified in this way can optionally be further optimized by xe2x80x9ccoatingxe2x80x9d with suitable materials with regard to a more targeted scent release, for which purpose preference is given to using wax-like polymers, such as, for example, polyvinyl alcohol.
The microencapsulation of the perfume oils can, for example, be carried out by the xe2x80x9ccoacervation methodxe2x80x9d using capsule materials made from, for example, polyurethane-like substances or soft gelatin. The spray-dried perfume oils can, for example, be prepared by spray drying an emulsion or dispersion comprising the perfume oil, where the carriers used can be modified starches, proteins, dextrin and vegetable gums. Inclusion complexes can be prepared, for example, by introducing dispersions of the perfume oil and cyclodextrins or urea derivatives into a suitable solvent, e.g. water. Extrusion products can arise by melting the perfume oils with a suitable wax-like substance and by extrusion with subsequent solidification, optionally in a suitable solvent, e.g. isopropanol.
In perfume compositions, the amount of 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention used is 0.05 to 50% by weight, preferably 0.5 to 20% by weight, based on the total perfume oil.
The perfume oils comprising the 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention can be used in concentrated form, in solutions or in the above-described modified form for the preparation of, for example, perfume extracts, eaux de parfum, eaux de toilette, aftershaves, eaux de cologne, pre-shave products, splash colognes and perfumed freshening wipes, and the perfuming of acidic, alkaline and neutral cleaners, such as, for example, floor cleaners, window cleaners, dishwashing detergents, bath and sanitary cleaners, scouring milk, solid and liquid WC cleaners, pulverulent and foam carpet cleaners, liquid laundry detergents, pulverulent laundry detergents, laundry pretreatment agents, such as bleaches, soaking agents and stain removers, fabric softeners, washing soaps, washing tablets, disinfectants, surface disinfectants, and of air fresheners in liquid or gel form or deposited on a solid carrier, aerosol sprays, waxes and polishes, such as furniture polishes, floor waxes, shoe creams, and bodycare compositions, such as, for example, solid and liquid soaps, shower gels, shampoos, shaving soaps, shaving foams, bath oils, cosmetic emulsions of the oil-in-water, water-in-oil and water-in-oil-in-water type, such as, for example, skin creams and lotions, face creams and lotions, sunscreen creams and lotions, aftersun creams and lotions, hand creams and lotions, foot creams and lotions, depilatory creams and lotions, aftershave creams and lotions, tanning creams and lotions, haircare products, such as, for example, hairsprays, hair gels, hairsetting lotions, hair rinses, permanent and semipermanent hair colorants, hair-shaping compositions, such as cold waves and hair-smoothing compositions, hair tonics, hair creams and lotions, deodorants and antiperspirants, such as, for example, underarm sprays, roll-ons, deodorant sticks, deodorant creams, products in decorative cosmetics, such as, for example, eyeshadows, nail varnishes, foundations, lipsticks, mascara, and of candles, lamp oils, joss-sticks, insecticides, repellents, propellants.
One important use of the 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention is in the perfuming of soaps and laundry detergents because of their stability in the alkaline range. In the case of the use in laundry detergent perfumings, the 1,4-dioxacycloalkan-2-ones and 1,4-dioxacycloalken-2-ones according to the invention are distinguished by a substantivity which is greater than that of fragrances used hitherto, i.e. by increased absorptive power and increased adhesion of the fragrance to the washed fibers.
The compounds below illustrate the invention: